Exploration of glassy state in Prussian blue analogues

Nattapol Ma, Ryo Ohtani, Hung M. Le, Søren S. Sørensen, Ryuta Ishikawa, Satoshi Kawata, Sareeya Bureekaew, Soracha Kosasang, Yoshiyuki Kawazoe, Koji Ohara, Morten M. Smedskjaer, Satoshi Horike

Research output: Contribution to journalArticlepeer-review

Abstract

Prussian blue analogues (PBAs) are archetypes of microporous coordination polymers/metal–organic frameworks whose versatile composition allows for diverse functionalities. However, developments in PBAs have centred solely on their crystalline state, and the glassy state of PBAs has not been explored. Here we describe the preparation of the glassy state of PBAs via a mechanically induced crystal-to-glass transformation and explore their properties. The preservation of short-range metal–ligand–metal connectivity is confirmed, enabling the framework-based functionality and semiconductivity in the glass. The transformation also generates unconventional CN vacancies, followed by the reduction of metal sites. This leads to significant porosity enhancement in recrystallised PBA, enabled by further accessibility of isolated micropores. Finally, mechanical stability under stress for successful vitrification is correlated to defect contents and interstitial water. Our results demonstrate how mechanochemistry provides opportunities to explore glassy states of molecular framework materials in which the stable liquid state is absent.

Original languageEnglish
Article number4023
JournalNature communications
Volume13
Issue number1
DOIs
Publication statusPublished - Dec 2022

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • General
  • Physics and Astronomy(all)

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